3-substituted-5, 6-alkyleneuracils



United States Patent 6 Claims. (Cl. 260260) R-N RN ,L LTJCHQD I 36 2) no0 where R is a substituted or unsubstituted cycloalkyl radicalcontaining 3 through 10 carbon atoms, a substituted or unsubstitutedcycloalkenyl radical containing 4 through 10 carbon atoms, or a /Ri-C-Rz radical where R is methyl or ethyl,

R is alkyl containing 1 through 5 carbon atoms, and R is hydrogen ormethyl, and

n is 3, 4 or 5.

Also included within the invention are salts of the uracils of Formula 1formed with such cations as sodium, potassium, lithium, and quaternaryammonium.

For Formula 1, illustrative radicals of the terms cycloalkyl andcycloalkenyl, are:

cyclopropyl cyclohexyl cyclohexenyl cyclopentyl cyclopentenyl norbornylnorboruenyl bicyclo (2,2,2) octyl bicyclo (2,2,2) octenyl cyclobutylcyclobutenyl hexahydroindanyl tetrahydroindanyl hexahydroindenylhexahydro-4,7-methanoindenyl tetrahydro-4,7-methanoindanylhexahydro-4,7-methanoindanyl decahydronaphthyl tetrahydronaphthyl Thecycloalkyl or cycloalkenyl radical representing R in Formula 1 may besubstituted with a substituent selected from the group consisting ofalkyl containing 1 through 4 carbon atoms, methoxy, chlorine andbromine.

The compounds of the present invention represent a new class ofherbicides offering farmers and property owners a new and elfectivemethod for the control of undesirable vegetation.

Certain of these uracils exhibit selective action in crops. By properlyselecting a compound of the invention and a rate and time ofapplication, weeds growing in fields of such economic crops as corn,cotton, asparagus, sugar beets, red beets, mangels, spinach, potatoes,peanuts and pineapple can be controlled. This selective activity isdescribed in more detail in the examples which follow.

These compounds are also useful for general Weed control on industrialsites, railroad rights-of-way, and areas adjacent to croplands.

The compounds of this invention are also effective agents for thecontrol of aquatic weeds, including algae.

The concentrations at which the compounds of this invention are to beused will vary according to the result desired, the type of vegetation,the formulation used, the mode of application, weather conditions,foliage density, and other similar factors. Since so many factors play arole, it is not possible to indicate a concentration suitable for allsituations. Generally, when they are used for pre-ernergence treatmentin crops, these compounds are used at concentrations of at least about0.5 pound of active ingredient per acre. Concentrations of from 0.5 to 3pounds per acre are preferred.

When used in non-crop applications, these compounds are used atconcentrations of from 10 to 30 pounds of active ingredient per acre.The optimum concentrations to be used in any particular application willbe readily apparent to one skilled in the art.

The compounds of this invention are strong absorbers of ultravioletradiation. For example, 3-cyclohexyl-5,6 trimethyleneuracil in additionto strong and absorption at about 220 m shows a broad absorption peaknear 270 m The extinction coeflicient is about 7,500. Consequentlycompounds of this invention are useful as ultraviolet screening agents.In a typical application a compound is milled into a vinyl plastic inorder to retard the deterioration of the plastic by sunlight.

The uracil compounds of Formula 1 can be prepared according to thefollowing equations:

In Equations 2 and 3 R, and n have the same meaning as in Formula 1; Ris an alkyl radical of 1-6 carbon atoms, H+ is an acid, and B- is abase.

The reaction sequence consists of two steps: first, the acid catalyzedcondensation of a l-substituted urea with an alkyl2-cycloalkanone-l-carboxylate to give the ureido intermediate; and,second, the alkaline ring closure of this intermediate to the salt ofthe uracil product, followed by treatment with acid to liberate the freeuracil.

The first step, illustrated by Equation 2, is best carried out bydissolving or suspending the l-substituted urea in a solvent such asxylene, benzene or a mixture of benzene and dioxane, and heating toreflux. To this solution is then added a mixture of the acid catalyst ina slight excess of the alkyl Z-cycloalkanone-l-carboxylate. Suitableacid catalysts are phosphoric, polyphosphoric, formic, chloroacetic, orLewis acids such as BF and AlCl The mixture is stirred and heated toreflux until the water, split out during the reaction and collected in asuitable apparatus, ceases to be given off. The clear solution isdecanted or filtered and then concentrated to give the intermediateureido derivative.

In the second step, illustrated by Equation 3 the ureido intermediate isdissolved in alcohol containing .a slight excess of base, preferably analkali metal alkoxide or hydroxide, and the solution is refluxed for ashort time. This step effects the ring closure. The salt of the uracilis obtained by concentrating this solution to dryness. The free uracilis prepared by acidifying an aqueous solution of the salt, and thenisolating the solid.

These compounds can also be prepared as described in Archives ofBiochem. and Biophys., 83, 141 (1959).

The salts of the compounds of Formula 1 are prepared by conventionalmethods such as dissolving the free uracil in an aqueuos or nonaqueoussolution of at least an equimolar amount of a base or basic saltcontaining the desired cation. For example, a sodium salt can beprepared by dissolving the uracil in water containing an equimolaramount of sodium hydroxide. The salt can then be isolated from thesolution by removal of the water.

The quaternary ammonium salts of the compounds of Formula 1 are preparedby reacting the uracil compound with an appropriate quaternary ammoniumhydroxide. Since these hydroxides are generally available in solution,the reaction is most conveniently carried out in the same solvent. Ifthe solvent-free salt is desired, it can be easily prepared by removingthe solvent.

Alternatively, the quaternary ammonium salts of the uracils can beprepared in a dry inert solvent such as toluene or xylene. The sodiumsalt of the uracil is first prepared and the appropriate quaternaryammonium halide is then added with stirring and, if necessary, mildheating. The sodium halide which forms is removed by filtration, leavingthe quaternary ammonium salt of the uracil in solution. If desired, thesolvent-free salt can be prepared by removing the solvent, preferably invacuo.

The compounds of the invention can be prepared for use by incorporatingthem with adjuvants.

The amount of herbicide in such preparations can vary over a wide rangeaccording to need. Generally speaking, they will contain from about 0.5%to by weight o f a uracil.

Powder and dust preparations can be made by mixing the compounds of theinvention with finely divided solids such as talcs, natural clays,pyrophillite, diatomaceous earth; flours such as walnut shell, wheat,redwood, soya bean and cotton seed; or inorganic substances such asmagnesium carbonate, calcium carbonate, calcium phosphate, sulfur andlime. These preparations are made by thoroughly blending the activeingredient and the solid. The particles in such preparations should beless than 50 microns in average diameter, preferably about 20 microns.

Water-soluble powders can be prepared by blending a suitable uracil oruracil salt with such water-soluble alkaline powders as silicates,carbonates, phosphates or hydroxides, and optionally with water-solublediluents such as urea or dextrose.

Granules and pellets can be made by mixing a finely divided uracil orsalt with a suitable clay such as kaolinite, montmorillonite oratt-apulgite, moistening this mixture with from 15 to 20% by weight ofWater, and then extruding the mass through a suitable die underpressure. The extrusions are cut into pro-determined lengths and thendried. These pellets can be granulated if desired.

Granules or pellets can also be prepared by spraying a suspension orsolution of a compound of the invention onto the surface of a preformedgranule of clay, vermiculite or other suitable granular material. If thecompound is in solution, it will penetrate into the pores of the granuleand so will adhere without the aid of a binding agent. When the activematerial is insoluble in the liquid and is carried as a suspension, itis preferable that a binding agent such as goulac, dextrin, swollenstarch, glue or polyvinyl alcohol be added. In either case, the granuleis then dried and ready for use.

The compounds of the invention can also be prepared in liquids. Waterand aliphatic .and aromatic hydrocarbons, especially those derived frompetroleum and having boiling points of from C. to 400 C. are preferred.Hydrocarbons having lower boiling points are less useful because oftheir undesirable volatilization characteristics and inflammability.These liquid preparations are made by dissolving the active in theliquid, or, if the active is insoluble in the liquid, by milling thecomponents in a mill such as a pebble mill until the particles haveaverage diameters of from 1 to 50 microns, preferably 5 to 20 microns.

The herbicidal preparations, whatever physical form they take, can alsocontain a surface-active agent. The surfactant renders the preparationsreadily dispersible in liquids and improves their action on waxy leavesand the like. For general application, surface-active agents are used inthe preparations at concentrations of from about 1 to 10% by weight.Levels of from 0.5 to 6 parts of surfactant for each part of uracil oruracil salt, however, give unusual and unexpected results. Preparationshaving these higher levels of surfactants show greater herbicidaleffectiveness than can be expected from a consideration of activity ofthe components used separately.

The term surface-active agent is intended to include Wetting agents,dispersing agents, suspending agents and emulsifying agents.Surface-active agents suitable for use are set forth in Detergents andEmulsifiers Annual, 1965, John W. McCutcheon, Inc., Morristown, NewJersey. Other surface-active agents which can be used in thesepreparations are listed in U.S. Patents 2,139,276; 2,412,510; 2,426,417;and 2,655,447.

The preparations can also contain adhesives, corrosion inhibitors,antifoam agents, dyes, and pigments, anticaking agents, and hard waterstabilizers.

The salts of the compounds of Formula 1 are especially advantageous foruse as herbicides because many are soluble in water and can be appliedas aqueous solutions.

The herbicidal compositions of this invention can be formulated tocontain two or more of the compounds of the'invention. They can also beformulated to contain other known herbicides in addition to the uracilsor their salts to give compositions which have advantages over theindividual components.

Among the known herbicides which can be combined with the compounds ofthe invention are:

Substituted areas 3 -(3,4-dichlorophenyl)-1,l-dimethylurea 3(4-chloropheny1)-1,l-dimethylurea 3-phenyl-1,l-dimethylurea3-(3,4-dichlorophenyl) -3-methoxy-1, l-dimethylurea 3- (4-chlorophenyl)-3 -Inethoxy-1, l-dimethylurea 3- 3 ,4-dichlorophenyl)-l-n-butyl-1-methylurea 3,4-dichlorophenyl) -1-methoxy-1-methylurea4-chlorophenyl) l-methoxy-l -methylurea (3 ,4-dich1orophenyl) -1, 1,3-trimethylurea 3- 3 ,4-dichlorophenyl)-1,1-diethylurea3-(p-chlorophenoxyphenyl)-1,1-dimethylurea These ureas can be mixed withthe compounds of the invention in proportions of from 1:4 to 4: 1,respectively, the preferred ratio being 1:2 to 2: 1.

Substituted triazines 2-chloro-4,6-bis(ethylamino)-s-triazine2-chloro-4-ethylamino-6-isopropylamino-s-triazine2-chloro-4,6-bis(methoxypropylamino)-s-triazine2-methoxy-4,6-bis(isopropylamino)-s-triazine2-ethylan1ino-4-(2-methoxyethylamine)-6-chloro-s triazine2-isopropylamino-4-methoxyethylamino-6-methylmercapto-s-triazine2-methylmercapto-4,6-bis (isopropylamino -s-triazine2-methylmercapto-4,6-bis(ethylamino)-s-triazine2-methylmercapto-4-ethylamino-6-isopropylamino-striazine2'-rnethoxy-4,6-bis (ethylamino) -s-triazine2-methoxy-4-ethylamino-6-isopropylamino-s-triazine2-chloro-4,6-bis(isopropylarnino)-s-triazine These triazines can bemixed with the compounds of the invention in proportions of from 1:4 to4:1, respectively, the preferred ratio being 1:2 to 2: 1.

Phenols Dinitro-o-sec-butylphenol and its salts Pentachlorophenol andits salts These phenols can be mixed with the compounds of the inventionin the proportions of 1:10 to 20:1, respectively, the preferred ratiobeing 1:5 to 5 1.

Cwrboxylic acids and derivatives The following carboxylic acids andderivatives can be mixed with the compounds of the invention in thelisted respective proportions:

2,3,6-trichlorobenzoic acid and its salts 2,3,5,6-tetrachlorobenzoicacid and its salts 2-rnethoxy-3,5,6-trichlorobenzoic acid and its salts2-methoxy-3,6-dichlorobenzoic acid and its salts3-amino-2,S-dichlorobenzoic acid and its salts3-nitro-2,5-dichlorobenz0ic acid and its salts2-methyl-3,6-dichlorobenzoic acid and its salts2,3-dichloro-6-methylbenzoic acid and its salts2,4-dichlorophenoxyacetic acid and its salts and esters2,4,S-trichlorophenoxyacetic acid and its salts and esters(2-rnethyl-4-chlorophenoxy)acetic acid and its salts and esters2-(2,4,5-trichlorophenoxy)propionic acid and its salts and esters2-(2,4,5-trichlorophenoxy)ethyl-2,2-dichloropropionate4-(2,4-dichlorophenoxy)butyric acid and its salts and esters4-(2-methyl-4-chlorophenoxy)'butyric acid and its salts and esters2,3,6-trichlorobenzyloxypropanol Mixed in a 1:20 to 8:1 ratio,preferably a 1:4 to 4:1 ratio.

B. 2,6-dichlorobenzonitrile Mixed in a 1:4 to 4:1 ratio, preferably a1:3 to 3:1 ratio.

C. Trichloroaceti-c acid and its salts G. 2,3,6-trichlorophenylaceticacid and its salts Mixed in a 1:20 to 8:1 ratio, preferably a 1:4 to 4:1ratio.

2-chloro-N,N-diallylacetamide Maleic hydrazide Mixed in a 1:2 to 10:1ratio, preferably a 1:1 to 5:1 ratio.

Inorganic and mixed inorganic-organic salts The following salts can bemixed with the uracils in the listed proportions:

Calcium propylarsonate Disodium monomethylarsonateOctyl-dodecylammoniummethylarsonate Dimethylarsinic acid Mixed in a 1:4ratio, preferably a 1:2 to 2:1 ratio.

B. Sodium arsenite Mixed in a 1:10 to- 40:1 ratio, preferably a 1:5 to

25:1 ratio.

Lead arsenate Calcium arsenate Mixed in a 150:1 to 600:1 ratio,preferably a :1 to 400: 1' ratio.

Sodium tetraborate hydrated, granulated Sodium metaborate Sodiumpentaborate Polychloroborate Unrefined borate ore, such as borascu Mixedin a 3:1 to 1500:1 ratio, preferably a 6:1 to l000:1 ratio.

E. Ammonium thiocyanate Mixed in a 1:10 to 20:1 ratio, preferably'a 1 :5to 5:1 ratio.

F. Sodium chlorate Mixed in a 1:1 to 40:1 ratio, preferably a 2:1 to20:1 ratio.

G. Ammonium sulfamate Mixed in a 1:1 to 100:1 ratio, preferably a 1:1 to50:1ratio.

Other organic herbicides The following herbicides can be mixed with theuracils in the listed respective proportions:

1,1'-ethylene-2,2-dipyridylium cation 1,l'-ethylene-4,4'-dipyridyliumcation Mixed in a 1:20 to 16:1 ratio, preferably a 1:5 to 5:1 ratio.

B. 3-amino-l,2,4-triazole Mixed in a 1:20 to 20:1 ratio, preferably a1:5 to 5:1

ratio.

C. 3,6-endoxohexahydrophthalic acid Mixed in a 1:4 to 20:1 ratio,preferably a 1:2 to 10:1 ratio.

D Diphenylacetonitrile N,N-dimethyl-a,u-diphenylacetamide N,N-din-propyl 2,6-dinitro-4-trifluoromethylaniline N,N-di (n-propyl)-2,6-dinitro-4-methylaniline Mixed in a 1:10 to 30:1 ratio, preferably a1:5 to 20: 1 ratio.

The compounds of the invention can be mixed with other substituteduracils, in the respective proportions listed below.

3-is0propyl-5-bromo-6-methyluracil 3-isopropyl-5-chloro-6-methyluracil3-sec-butyl-5-bromo-6-methyluracil 3-sec-butyl-5-chloro-6-methyluracil3-cyclohexyl-S-bromo-6-methyluracil 3-cyclohexyl-5-chloro-6-methyluracil 3-tert-butyl-5 -bromo-6-methyluracil3-tert-butyl-5-chloro-6-methyluracil Mixed in a 1:6 to 6:1 ratio,preferably a 1:4 to 4:1 ratio.

3-cyclohexyl-6-rnethyluracil 3 cyclohexyl-6-ethyluracil3-cyclohexyl-6-sec-butyluracil 3-cyclohexyl-fi-propyluracil3-cyclopentyl-6-rnethyluracil 3-cyclohexy1uracil Mixed in a 1:6 to 6:1ratio, preferably a 1:4 to 4:1 ratio.

3-isopropyl-5-bromouracil 3-sec-butyl-5-bromouracil3-sec-butyl-S-chlorouracil 3-cyclohexyl-S-bromouracil3-cyclohexyl-S-ohlorouracil Mixed in a 1:4 to 4:1 ratio, preferably a1:2 to 2:1 ratio.

3-isopropyl-1-trichloromethylthio-5-bromo-6-methyluracil3-cyclohexyl-1-trichloromethylthio-5-bromo-6-methyluracil 3-sec-butyll-acetyl-S-bromo-6-rnethyluracil 3-isopropyl-l-acetyl-5-bromo-6-rnethyluracil3-isopropyl-1-trichloromethylthio-5-chloro-6-methyluracil Mixed in a 1:4to 4:1 ratio, preferably a 1:2 to 2:1 ratio.

Many of the above materials, e.g. borates, arsonates, dinitrosec-'butylphenol, etc., act as bactericides and fungicides. Addition ofthese compounds, or compounds of similar action, inhibit the degradationand inactivation of the herbicidal uracils by soil micro-organisms, and,consequently increase their usefulness as herbicides.

EXAMPLES This invention will be better understood by the followingexamples concerning the preparation of the compounds of the inventionand the preparation and use of herbicidal compositions containing thesecompounds.

PREPARATION OF COMPOUNDS Example 1.Preparati0n 0f 3-is0pr0pyl-5,6-trimethyleneuracil A mixture of 404 parts by weight ofisopropylnrea, 686 parts by weight of ethylZ-cyclopentanone-l-carboxylate, 40 parts 'by weight of phosphoric acid,1000 parts by weight of diox-ane, and 879 parts by weight of benzene isstirred at reflux for 4 hours. During this time, the water given oflf bythe reaction is trapped out. The solvent is stripped at reduced pressureand a portion of the resulting solid is recrystallized from cyclohexaneto give 2-(3-isopropylureido)-1-cyclopentene carboxylic acid, ethylester.

The remaining unrecrystallized solid is dissolved in 2360 parts byweight of absolute alcohol containing 248 parts by weight of sodiummethoxide, and is refluxed for 10 minutes. The solvent is stripped atreduced pressure and the residue dissolved in water, cooled, andacidified. The solid is filtered off, dried, and recrystallized fromethanol to give the desired 3-isopropyl-5,6-trimethyleneuracil, meltingat 222223.5 C.

Example 2.-Preparati0n of 3-cyclohexyl- 5,6-trimethyleneuracil A mixtureof 343 parts by weight of ethyl 2-cyclopentanone-l-c-arboxylate, 284parts by weight of cyclohexylurea, 10 parts by weight of p-toluenesulfonic acid, and 1750 parts by weight of xylene is stirred at refluxfor 6 hours. During this time the water given olf by the reaction istrapped out. The solvent is stripped from the resulting solution atreduced pressure. The residue is then dissolved in 793 parts by weightof absolute ethyl alcohol.

To this solution is added a mixture of parts by weight of sodiummethoxide in 400 parts by weight of absolute ethyl alcohol. The mixtureis then refluxed for 10 minutes. The solvent is stripped from thismixture and the resulting solid is dissolved in 3000 parts by weight ofwater.

This solution is cooled, acidified with excess hydrochloric acid and thesolid is filtered oif. Recrystallization of this solid fromdimethylformamide gives light gray crystals of the desired uracil,melting at BIO-313 C.

The compounds listed in the following table can be prepared according tothe procedures of Examples 1 or 2 by substituting equivalent amounts ofthe listed ureas and alkyl-2-cycloalkanone-l-carboxylates for those usedin the examples:

the two solid components in water. The product can be readily diluted touse levels and sprayed.

ide and 100 parts by weight of Water is added 58 parts by Weight of3-isopropyl-5,6-trimethyleneuracil. This slurry is heated and stirreduntil the solids are completely dissolved. The sodium salt of the uracilseparates on cooling. More of the solid can be forced out of solution bydilution with acetonitrile. The salt is filtered 0E and 'dried.

Example 4.--Preparati0n of 3-cycl0hexyl-5,6-trimethyleneuracil,tetrabutylammonium salt A mixture containing 234 parts of3-cyclohexyl-5,6- trimethyleneuracil and 865.8 parts of a one-molarsolution of tetrabutylammonium hydroxide in methanol is stirred andheated slightly until solution is complete. The solvent is removed bydistillation under reduced pressure. The resulting white solid isessentially pure 3-cyclohexyl- 5,6-trirnethyleneuracil,tetrabutylammonium salt.

Other quaternary ammonium salts can be similarly prepared by reactingequivalent amounts of an appropriately substituted uracil and a suitablequaternary ammonium hydroxide. The following compounds can be preparedin this fashion: 3-cyclopentenyl-5,6-tetramethyleneuracil,tetramethylammonium salt 3-bornyl-5,6trimethyleneuracil,trimethylbenzylammonium salt 3-isopropyl-5,6-trimethyleneuracil,trimethyldodecylammonium salt HERBICIDAL COMPOSITIONS-LIQUIDFORMULATIONS Example 5.Aque0us concentrate A.'An aqueous concentrate isprepared by dissolving Substituted Urea Parts by Ester of theCycloalkanone Carboxylate Parts by Substituted Uracil Product WeightWeight 1-(2-heptyl) urea 158 Methyl 2-cyelopentanoue-l-earboxylate 1563(2heptyl)-5, fi-trimethyleneuracil. 1-(3-pentyl) urea ..do 1563-(3-pentyD-5, fi-trimethyleneuracil. Tert-butylurea 116 Ethyl2-eyelohexanone-l-carboxylate 187 3-tert-butyl-5,d-tetramethyleneuraeil. Cyclooctylurea Methyl2-cyclopentauone-l-carboxylate.. 156 3-cycloocty1-5,fi-trimethyleneuracil. Cyelopentenylurea 126 do 1563-cyclopentenyl-5,6-trimethyleneuraeiL Fenehylurea 216 do 1563-fenchyl-5, G-trimethyleneuracil. Cyclohexenyl urea 138 Ethyl2-eyeloheptanone-1-carb0xylate- 202 3-cyclohexenyl-5,6-pentamethyleneuraeiL Norbornenylurea .1 150 ..-do 202 3-norb0rnenyl-5,6'pentamethyleneuraeil. Oyclobutylurea 114 do 2023-cyclobutyl-5,6pentamethyleneuracil. Cyclopentylurea 128 Ethyl2-eyclohexanone-1-carboxylate-. 187 3-cyclopentyl-5,6-tetramethyleneuraeiL 1-(4-methoxyeyclohexyl) urea.- 172 do 1873-(4-methq rycye1ohexyD-5,fi-tetramethyleneuraei Cyclooctenylurea 168Methyl 2-eyc1ohexanone-l-carboxylate 162 3-cyelooctenyl-5, fitetramethyleneuraciL Carvacrylurea.-. 191 Methy2-cyelopentanone-l-earboxylate 156 3-earvacryl-5, fi-trimethyleneuraeil.Isopropylurea 102 Methyl 2-cyelohexan0ne-1-carboxylate. 1623-iS0pr0pyl-5, fi-tetramethyleneuraeil. Cycloheptenylurea 156 Ethyl2-eycloper1tanone-1-carboxylate. 187 3-cyel0heptenyl-5,G-trimethyleneuracil. Norbornylurea 152 Methyl2-cyclopentanone-l-carboxylate 15G 3-n0rbornyl5, titrimethyleneuraeil.Bicyclo(2,2,2)octylurea 168 .do 187 3-[b1cyp l0 (2, 2,2)0Ctyl]-5,6-pentarnethyleneuraci Hexahydr0-4, 7-methano-indanyl 195 do187 (3-hexahydro-4, 7-methan0-i11danyD-5 urea. pentamethyleneuracil.Bornylurea .do 156 3-bornyl-5, G-trimethyleneuraeil. l-cyclohexyl ureaEthyl 2-cyclohexanone-l-carboxylate 156 3-cyclohexyl-5, G-tetramethyleneuracil. Norbornylurea. 174 3-norbornyl-5, fi-tetramethyleneuraeil.Cyelopropylurea- 162 3-eyc1opropyl-5, G-trimethyleneuraciLHexahydroindanyl-urea 162 3-hexaliydro1ndanyl-5, 6trimethylene- UIflCl1-[3-(3-methyoety1)]-urea .1 190 ...do 162 3-[3(3- I]nethy1octyl)]-5,6-trimethyleneuraei Cyclobutylurea 112 do 162 3-cyclobutenyl-5,6-trimethyleneuraeiL Decahydronaphthylurea 196 .....(10 162 3-de0a11lydr0naphthyl-5, G-trimethyleneurac 1-(4-isopropylcyclohexyl)uream ..do162 3-(4-istgflopylcyclohexyl)-5,6-trimethyleneurae 1-(1-ethylhexyl)urea158 do 162 3-(1-ethylhexyD-5, trtrimethyleneuraeil. 1-(1,l-dimethyl-butyDuree 144 Ethyl 2-eyclohexanone-l-carboxylate 202 3-(1,l-dlimethylbutyb-fi, G-tetramethyleneuraei 1-(3a, 4, 5, 6, 7,7a-hexahydro-4, 7- 196 Ethyl 2-cyelopentanone-1-carboxylate 1. 1623-(3a, 4, 5, 6, 7, 7a-hexahydro-4, 7-methanomethano-5-idenyl)urea.5-1denyl)-5, G-trimethyleneuraeil.

Do 196 Ethyl 2-cyclohexanone bcarboxylate 187 3-(3a, 4, 5, 6, 7,7a-hexahydro-5-idenyly5 tetramethyleneuracil. Bicyclooctenylurea 166 d0187 3-(bieyclooctenyD-5,fi-tetramethyleneuracil 1-(4-buty1eyclohexyD-urea 198 .do 187 3-(4-b1htylcyclohexyD-5,fi-tetramethyleneurac 1-(2-chlorocyclohexyl)-urea 173 Ethyl2-cyclopentanone-l-carboxylate 162 3-(2-ehlorocyclohexyl)-5,G-trimethyleneuraei 1.(2.bmmocyc10hexy1).urea 222 .do 1623-(2-brqmocyclohexyD-5, G-trimethyleneuraci Example 3.-Preparation of3-z's0pr0pyl-5,6-trimethylene- Per ent uracil, sodium salt3-sec-amyl-5,6-trimethylene uracil, potassium salt 5 Int-Q a solution of12 parts by weight of sodium hydmX- g lauryl sulfate 9 ater 4 Thisaqueous concentrate is applied with a pressuretype hand sprayer. Threepounds of active ingredient per acre in 40 gallons of water givesexcellent preemergence control of foxtail, Watergrass, Johnson grassseedlings in sugar cane.

B. Thefollowing substituted uracils in equivalent amounts can also beformulated as aqueous concentrates according to this procedure:

These formulations, applied at the rate of 20 pounds (active) in 100gallons of water to weeds growing around 11 bridge abutments, giveexcellent control of wild barley, bedstraw, hedge bindweed, wild carrot,cheat grass, cocklebur, dog fennel and goose grass.

Example 6.A queous suspension The following ingredients are mixed andpebble-milled or sand-milled until substantially all the particles ofthe active material are under microns in size. The resulting stablethixotropic suspension does not cake on storage and is readily dilutedwith water to form a very slow settling suspension which requires noagitation during application.

Percent 3-isopropyl-5,6-tetramethyleneuracil 28.0 Sodium ligninsulfonate 15.0 Hydrated attapulgite 2.0 Disodium phosphate 0.8 0.5

Percent 3-cyclohexyl-5,6-trimethyleneuracil 22.503-cyclohexyl-5-bromo-6-.rnethyluracil 7.50 Sodium lignin sulfonate 15.00Hydrated attapulgite clay 1.75 Water 52.95-52.65 O.300.60

NaOH (as needed) The mix is wet-milled until all particles are belowmicrons in size. The pH of the slurry is then adjusted to about 8.5.

This formulation gives exceptional control of vegetation aroundwarehouses and industrial sites. It is dispersed in sufficient water togive good coverage of the area to be sprayed. Applied at the rate of 30pounds of active ingredients per acre, it gives good control of existingweeds and keeps the area weed-free. Good control of such troublesomeweeds as crabgrass, fall panicum, mares-tail, goatweed, smartweed,spotted spurge, morning glory, ragweed, pigweed, lambs quarters,buttonweed, foxtail, broomsedge, and Russian thistle is obtained.

Example 8.-Emulsifiable oil An emulsifiable oil is prepared by mixingthe components to give an homogeneous solution. This solution can thenbe emulsified in water for application.

Percent 3-(3-pentyl)-5,6-tetramethyleneuracil 10.0 Alkyl aryl polyetheralcohol 2.5 2.5

Oil soluble petroleum sulfonate Example 9.Oil dispersions Percent3-cyclohexyl-5,6-trimethyleneuracil 12.5

3- 3 ,4-dichlorophenyl l l-dimethylurea 12.5 Parafiinic hydrocarbon (atleast 90% unsulfonatable) 72.0

Soya lecithin These components are mixed together and then wetmilleduntil the particles are below 10 microns in size. The resulting oilsuspension can be diluted further with oil for application.

This formulation is dispersed in 80 gallons of diesel oil and sprayed,in a blanket treatment, on vegetation 12 and bare areas along railroadballast. It is sprayed at a rate of 30 pounds of active ingredients peracre. Good control of Bermuda grass, ragweed, goldenrod, smartweed,seedling Johnson grass, spotted spurge, dogbane, and fiower-of-an-houris obtained.

Example 10.-Oil dispersion Percent 3-sec-butyl-5,6-trimethyleneuracil20.0 2-(2,4,5-trichlorophenoxy)propionic acid 5.0 Diesel oil 75.0

These ingredients are mixed and then wet-milled until the particles ofuracil are below 10 microns in size.

This formulation is used for the control of a wide variety of woody andherbaceous perennial weeds and grasses along highway rights-of-way.Dispersed in No. 2 fuel oil, it is sprayed at 15-20 pounds per acre ofactive ingredients on dense growths of weeds and brush on highwayshoulders. Honeysuckle, brambles, water grass, goldenrod, ragweed, leafyspurge, seedling sassafras, maples, sweet gum, and poison ivy arecontrolled.

Example 11.-Oil dispersion Percent 3-cyclohexyl-5,6-tetramethyleneuracil20.0 2,3,6-triehlorobenzoic acid 10.0 Diesel oil 70.0

These components are mixed and then wet-milled until the insolubleparticles are under 10 microns in size.

This formulation is dispersed in gallons of herbicidal oil and sprayedalong an oil pipeline at the rate of 30 pounds of active ingredients peracre. Excellent control of leafy spurge, bindweed, panic grass, bigbluestern, purpletop, poison ivy, quack grass, seedling oaks, maples,sweet gum, ragweed, goldenrod, honeysuckle, and brambles is obtained.The area is kept clear of troublesome weeds for an extended period.

SOLID FORMULATIONS Example 12.-Tank mix Percent3-cyclohexyl-5,6-tetramethyleneuracil 80.00 Alkyl naphthalene sulfonicacid, Na salt 1.75 1.00

Partially desulfonated sodium lignin Attapulgite clay 17.25

Example 13.-Tank mix A wettable powder is prepared by blending andmicropulverizing the following components:

Percent 3-cyclohexyl-5,6-trimethyleneuracil 80.00 Alkyl naphthalenesulfonic acid, Na salt 1.75 Partially desulfonated sodium ligninsulfonate 2.00

Attapulgite clay 17.25

This wettable powder and an emulsifiable oil containing 6 pounds pergallon of N,N-dipropylthiolcarbamic acid, ethyl ester are added to aspray tank to form a dilute mixture, in water, of A. to 1%. pounds ofuracil formulation and /2 gallon of the ester formulation per 100gallons.

This dilute suspension-emulsion is applied at the volume rate of 100gallons per acre t0 spring-seeded alfalfa. Good control of such weeds aschickweed, smartweed, portulaca, penny cress, yellow rocket, shepherdspurse,

ragweed, redroot pigweed, crab grass, annual bluegrass, and henbit isobtained.

Example 14.Tank mix Percent 3-sec-butyl-5,6-trimethyleneuracil 60.0Mixed polyoxyethylene esters of fatty acids and oilsoluble petroleumsulfonates 5.0

Attapulgite clay 35.0

Percent 3-cyclohexyl-5,6-trimethyleneuracil 80. Sodium dioctylsulfosuccinate 1.75 Partially desulfonated sodium lignin sulfonate 1.00

Calcined, non-swelling montmorillonoid type clay (Pikes Peak Clay) 17.25

A wettable powder is prepared by blending the components and thenmicropulverizing them until the particles of the active ingredient aresubstantially all under 50 microns in size, and then reblending tohomogeneity.

When applied at 1 pound of active ingredient per acre in 40 gallons ofwater, this formulation gives excellent pre-emergence control of crabgrass, foxtail, cocklebur, lambs quarters, and burdock in a newlyplanted field of cotton. One to three pounds of active ingredient peracre gives good weed control in asparagus, sugar cane, and pineapple.One to two pounds per acre gives excellent pre-emergence control ofannual weeds such as crab grass, foxtail, wild mustard, ryegrass, andvelvetleaf in a newly planted field of spinach.

The following uracils can be similarly formulated, and when-used inherbicidally equivalent amounts, will give good general weed control:

3-norbornyl-5,6-trimethyleneuracil3-cycloheptyl-1,5,6-trimethyleneuracil3-cyclooctyl-5,6-trimethyleneuracil Example 16.Wettable powder Awettable powder is prepared by blending the following components,micropulverizing them until substantially all particles are under 50microns in size, and then reblending:

Percent 3-sec-butyl-5,6-trimethyleneuracil 80.00 Low viscositymethylcellulose 0.25 Alkyl naphthalene sulfonic acid, Na salt 1.75Disodium phosphate (corrosion inhibitor) 0.8

Attapulgite clay 17.20

The following powder is prepared in the same manner as Example 28, butin addition is passed through an air attrition mill, such as anair-reductionizer, to reduce the particle size to under 10 microns:

Percent 3-tert butyl-5,6-trimethyleneuracil 80.0 Dioctyl sodiumsulfosuccinate concreted with sodium benzoate (Aerosol OTB) 2.0Partially desulfonated sodium lignin sulfonate 1.0 Calcined,non-swelling montmorillonoid type clay (Pikes Peak clay) 17.0

This composition is used for pro-emergence application in agriculturalcrops such as sugar cane, asparagus, and safilower. It is dispersed in40 gallons of water and sprayed with a pressure sprayer. At 0.5 to 2.0pounds of active ingredient per acre, excellent control of pig weed,lambs quarters, purslane, mustard, crab grass, foxtail, and water grassis obtained.

Example 18-Wettable powder The following are blended, thenmicropulverize-d until the particles are below 50 microns in diameter,and reblended:

Percent 3-bornyl-5,6-trimethyleneuracil 25 Alkylnaphthalene sulfonicacid, sodium salt 1 Partially desulfonated sodium lignin sulfonate 1Attapulgite clay 75 This wettable powder is suspended in water at aconcentration of 15-20 pounds of active ingredient per 100 gallons ofWater. This suspension is sprayed at the rate of 100 gallons per acrefor control of crab grass, Water grass and lambs quarters growing aroundtelephone poles.

Example I9.Wettable powder Percent3-(norbornenyl)-5,6-trimethyleneuracil 75.0 Dioctyl sodiumsulfosuccinate 0.5 Ditertiary acetylenic glycol 0.5 Coconut acid esterof sodium isethionate 0.5 Precipitated sodium silico aluminate 23.5

These components are mixed, and micropulverized until the particles areless than 50 microns in diameter.

An application of this formulation at 25 pounds (active) in gallonswater controls beggar tick, wild mustard, lambs quarters, plantain,velvetleaf, annual bluegrass, Canadian bluegrass, crab grass, foxtail,and seedling Johnson grass growing around radar installations.

The following compounds can be formulated in a similar fashion. Whenused in the same Way, at equivalent rates, they give good weed control.

3- bicyclo [2,2,2] oct-5-en-2-yl -5,6-trimethyleneuracil 3- 5,6,7,8-tetrahydronaphthyl -5 ,6-tri'methyleneuracil3-isopropyl-5,6-trimethyleneuracil 3-cyclohexyl-5,6-pentamethyleneuracilExample 20.Wettable powder Percent 3-cyclohexyl-5,6-tri-methyleneuracil16.0 3,6-endoxohexahydrophthalic acid 64.0 Polyoxyethylene tall oil acidester 3.0 Low viscosity polyvinyl alcohol 0.5 Synthetic fine silica 16.5

This wettable powder is prepared by blending the components and thenmicropulverizing the mixture until the particles are under 50 microns insize.

This formulation is dispersed in water and sprayed preemergence at 5pounds of active ingredients per acre on a planting of red table beets.Excellent control of crab grass, chickweed, annual morning glory,carpetweed, purslane, smartweed, lambs quarters, ragweed, blacknightshade, giant foxtail, and velvet leaf is obtained. The crop showsno visible injury.

Example 2I.Wettable powder Percent 3-sec-butyl-5,6-trimethylcneuracil40.0 3-(4-chlorophenyl)-1,l-dimethylurea 20.0 Alkyl naphthalenesulfonate, Na salt 1.5 Low viscosity methyl cellulose 0.5 Attapulgiteclay 38.0

A Wettable powder is prepared by blending these components and thenmicropulverizing the mixture until the particles are below 50 microns insize.

This formulation controls weeds along railroad rightsof-way. Applied inthe spring in about 100 gallons of water and at the rate of 25 pounds ofactive ingredients per acre, the formulation gives good control ofannual ryegrass, bromegrass, ragweed, henbit, goldenrod, field daisy,buckhorn plantain, water grass, and volunteer rye.

Example 2Z.Wettable powder Percent3-cyc1ohexyl-5,6-tetrarnethyleneuracil 40.02-chloro-4-ethylamino-6-isopropyl-amino-s-triazine 20.0 Dioctyl sodiumsulfosuccinate concreted 85-l5 with sodium benzoate 1.0 Low viscositymethyl cellulose 0.3 Calcined montmorillonoid clay 38.7

A wettable powder is prepared by blending these ingredients and thengrinding them until the particles are below 50 microns in size.

A tractor-mounted sprayer which sprays four rows at a time is used toapply this formulation to a field of potatoes, before the potatoesemerge. The formulation is used at a rate of 3 pounds of activeingredients per acre. Such Weeds as crab grass, chickweed, smartweed,purslane, giant foxtail, annual morning glory, Johnson grass seedlings,barnyard grass, bedstraw, and henbit are controlled without visibleinjury to the potatoes. Excellent yields of potatoes are obtained, withminimum cultivation.

Example 23.Wettable powder Percent1-(3,4-dichlorophenyl)-3,3-dimethylurea 80.00 Low viscosity methylcellulose 0.25 Alkyl naphthalene sulfonic acid, sodium salt 1.75Disodium phosphate 0.80 Attapulgite clay 17.20

These ingredients are blended, micropulverized until all particles arebelow 50 microns in diameter, and then reblended.

Percent 3-cyclohexyl-5,6-trimethyleneuracil 80.00 Alkylnaphthalenesulfonic acid, sodium salt 1.75 Partially desulfonated sodium ligninsulfonate 1.00 Calcined non-swelling montmorillonite clay 17.25

These ingredients are blended, micropulverized until all particles arebelow 50 microns in diameter, and then reblended.

Nine parts (active) of the uracil formulation are mixed with one part(active) of the urea formulation.

This mixture, applied at 1.25-2 pounds (total active herbicides) peracre in 40 gallons of water to a new planting of sugar beets, givesexcellent control of foxtail, crab grass, barnyard grass, pigweed, lambsquarters, ragweed and velvetleaf.

Example 24.Pellets Percent 3-cyclohexyl-5,6-tetramethyleneuracil 25Anhydrous sodium sulfate 10 Sodium lignin sulfonate 10 Ca, Mg bentonite55 These components are blended and micropulverized, then moistened with18-20% water and extruded through small die holes. The extrusions arecut as formed to give small pellets which are then dried.

These pellets control both annual and perennial weeds along highwayguard rails, around bridges, cyclone fences, and highway signs whenapplied by hand at levels of 15 to 30 pounds of active ingredient peracre.

The following uracils, when formulated in this manner and used atherbicidally equivalent rates, give good weed control:

3-tert-butyl-5 ,6-pentameth yleneuracil 3 -cyclopropyl-5,6-tetramethyleneuracil 3-cyclopentyl-5 ,6-tetramethyleneuracil 3-norbornyl-5 ,6-tetramethyleneuracil 3- (decahydro- 1,4,5,8-dimethanonaphth-2-yl -5,6-trimethyleneuracil 3-sec-butyl-5,6-pentamethyleneuracil Example 25.Pellets Percent3-cyclohexyl-5,6-trimethyleneuracil 43-(p-chlorophenyl)-1,l-dimethylurea 2 Kaolin clay 37 Mississippisub-bentonite clay 37 Sodium sulfate 10 Sodium lignin sulfonate 10Example 26.Pellets Percent 3-isopropyl-5,6-trimethyleneuracil 3.33Phenyldimethylurea 6.67 California sub-bentonite clay 80.00 Sodiumsulfate, anhydrous 1000 These ingredients are blended, micropulverized,pugrnilled with 15 %-20% Water, and extruded through 4;- inch holes. Theextrusions are cut into /g-inch lengths, dried, and screened.

This formulation is used to control all vegetation in a fire lane. Thepellets are distributed from the air in remote areas of the fire lane atthe rate of 40 pounds of active ingredients per acre. Excellent controlof elm, sweet gum, oaks, maples, brambles, goldenrod, blackeyed Susan,and honeysuckle is obtained.

Example 27.-Pellers Percent 3-cyclohexyl-5,G-trimethyleneuracil 6.673-sec-butyl-5-chloro-6-methyluracil 3.33 Sodium sulfate, anhydrous 10.00Californiia sub-bentonite clay 80.00

These ingredients are pelletized in the manner of Example 26.

This formulation keeps lumber yards free of weeds. The pellets aredistributed in the spring with a seeder at 20 pounds (active) per acre.The lumber-yard stacking area is kept free of such pernicious Weeds ascrab grass, ragweed, pigweed, Russian thistle, fall panicum, goat weed,cheat grass, and seedling Johnson grass.

Examples 28.Granules Percent 3-isopropyl-S,6-trimethyleneuracil, Na salt5 8-15 mesh granular, expaned vermiculite This granular composition isprepared by dissolving the active material in water and spraying it uponthe granules while they are being tumbled. The granules are then dried.

These g anules are applied at 25 pounds of active ingredient per acre tomixed annular and perennial vegetation growing under cyclone fences,around highway markers, along fence rows, and around oil tankinstallations. Excellent weed control is obtained.

The following compounds can be formulated in a like manner, and whenused in herbicidally equivalent amounts, will give good weed control:

3-cyclopentyl-5,6-pentamethyleneuracil, tetramethylammonium salt3-cyclohexyl-5,6-trimethyleneuracil, tetramethylammonium salt3-sec-butyl-5,6-trimethyleneuracil, tetrabutylammonium salt3-tert-butyl-5,6-trimethyleneuracil, tetrabutylammonium salt3-sec-amyl-5,6-trimethyleneuracil, sodium salt3-isopropyl-5,6-trimethyleneuracil, trimethylbenzylammonium salt 3-(a-decahydro- 1 ,4-5,8-dimethanonaphthyl -5,6-trimethyleneuracil, sodiumsalt Examples 29.Granules The following composition is prepared bydissolving the active ingredient in water and spraying the solution uponthe attapulgite granules while they are being tumbled. The granules arethen dried.

Percent 3-isopropyl-5,6-trimethyleneuracil, sodium salt 4 Granular 8-15mesh attapulgite clay 96 These granules are applied by hand or byspecial spreaders at 2.5 pounds of active ingredient per acre for thepreemergence control of annual weeds in potatoes. They control crabgrass, chickweed, barnyard grass, goose grass, foxtail, velvetleaf, andgerminating Johnson grass without visible injury to the crop.

Examples 30.-Granules Percent 3-cyclohexyl-5,6-trimethyleneuracil 16.672 ethylamino 4 isopropylamino-6-methylthio-striazine 8.33 Kaolin clay72.00 Low viscosity methyl cellulose 3.00

The ingredients are blended and micropulverized, then pug-milled with towater, and moist-granulated. After drying, the granules are screened to8- 30 mesh.

These granules are distributed along the bank of a drainage canal.Applied at 120 pounds of granules per acre, good control of an existingrank growth of canary grass, smartweed, pigweed, and goldenrod isobtained.

Example 31 .Granules Percent 3-isopropyl-S,6-trimethyleneuracil 2.00Polyoxyethylene tall oil acid ester 0.02 Sodium chlorate 40%, sodiummetaborate 60% 97.98

The surfactant and uracil are first mixed and micropulverized, thensuspended in water and sprayed on the remaining granular componentswhile they are being tumbled.

18 These granules are distributed by hand at the rate of about 1.5pounds per square feet around airport signal lights. Excellent controlof Johnson grass, brambles, poison ivy, honeysuckle, pigweed, ragweed,bindweed, Bermuda grass, cheat grass, and big 'bluestem is obtained.

Example 32.-Granules Percent 3-cyclohexyl-5,6-trimethyleneuracil 1.0Trichloroacetic acid, sodium salt 3.0 Attapulgite clay, granular 1530mesh 96.0

(a) Compounds of the formula 0 o H H L I (out). IEOHZ). 0 N HO where:

R is cycloalkyl containing 3 through 10 carbon atoms, substitutedcycloalkyl containing 3 through 10 carbon atoms wherein said substituentis selected from the group consisting of alkyl containing 1-4 carbonatoms, chlorine, bromine, and methoxy; cycloalkenyl containing 4 through10 carbon atoms; substituted cycloalkenyl containing 4 through 10 carbonatoms wherein said substituent is selected from the group consisting ofalkyl containing 1-4 carbon atoms, chlorine, bromine, and methoxy, or

wherein: R is methyl or ethyl, R is alkyl containing 1 through 5 carbonsatoms, and R is hydrogen or methyl, and n is 3, 4, or 5; and

(b) the sodium, potassium, lithium, and alkyl quaternary ammonium saltsof the compounds of (a). 2. 3-cyclohexyl-5,6-trimethyleneuracil. 3.3-isopropyl-5,6-trimethyleneuracil. 4.3-sec-butyl-5,6-tetramethyleneuracil. 5.3-cyclohexyl-5,6-tetramethyleneuracil. 6.3-tert-butyl-5,6-trimethyleneuracil.

No references cited.

NICHOLAS S. RIZZO, Primary Examiner. M. U. OBRIEN, F. A. MIKA, AssistantExaminers.

1. COMPOUND SELECTED FROM THE GROUP CONSISTING OF: (A) COMPOUNDS OF THEFORMULA: